Polyhalopolyhydropolycyclicdicar-boxylic acid imides

ABSTRACT

NOVEL COMPOSITIONS OF MATTER COMPRISING HALOARYL IMIDES OF POLYHALOPOLYHYDROPOLYCYCLICDICARBOXYLIC ACIDS AS EXEMPLIFIED BY A,A&#39;&#39;-BIS-(5,6,7,8,9,9-HEXACHLORO-1,2,3,4, 4A,5,8,8A-OCTAHYDRO-5,8-METHANO-2,3-NAPHTHALENEDICARBOXIMIDO)-2,3,5,6 -TETRACHLORO-P-XYLENE ARE USEFUL AS ADDITIVES FOR PLASTICS, POLYMERS, RESINS, ETC. WHEREBY FLAMEPROOF OR FIRE-RETARDANT PROPERTIES ARE ADDED THERETO.

United States Patent 3,574,230 POLYHALOPOLYHYDROPOLYCYCLICDICAR- BOXYLICACID IMIDES Henry A. Cyba, Evanston, Ill., assignor to Universal OilProducts Company, Des Plaines, II].

No Drawing. Filed Sept. 5, 1968, Ser. No. 757,764 Int. Cl. C07d 27/52US. Cl. 260-326 10 Claims ABSTRACT OF THE DISCLOSURE Novel compositionsof matter" comprising haloaryl' imides ofpolyhalopolyhydropolycyclicdicarboxylic acids as exemplified byot,ot'-blS-[5,6,7,8,9,9-h6XaChlOrO-l,2,3,4, 4a,5,8,8a octahydro5,8-methano-2,3-naphthalenedicarboximido]-2,3, S,6-tetrachloro-p-xyleneare useful as additives for plastics, polymers, resins, etc. wherebyflameproof or fire-retardant properties are added thereto.

This invention relates to novel compositions of matter comprisinghaloaryl imide's of polyhalopolyhydropolycyclicdicarboxylic acids. Morespecifically, the invention relates to these compositions of matter andto their use thereof as additives to polymers or other chemicalcompounds whereby certain desirable physical characteristics areimparted to these compounds.

It has now been discovered that novel compositions of matter comprising,as hereinbefore set forth, haloaryl imides ofpolyhalopolyhydropolycyclicdicarboxylic acids may be prepared byreacting a halo-substituted xylenea,u'-diamine or a halo-substitutedp-ditolyl ether-, thioether-, amineor alkane-u,a-diamine with apolyhalopolyhydropolycyclicdicarboxylic acid or anhydride thereof withincertain mole ratios to prepare the desired products. For purposes ofthis invention, the term haloaryl imides as used in the presentspecification and appended claims will refer to both monoand bis-imidesas well as monoand di-aryl compounds. These novel compositions of matterwill, as hereinbefore set forth, be useful as additives to plastics,polymers, copolymers, terpolymers, resins, elastomers, rubbers, textilesand fibers, both naturall yoccurring and synthetic in nature, such ascotton,

polymers, polymethacrylates and co-polymers with styrene, butadiene,acrylonitrile, etc, epoxy resins, acrylonitrile-butadiene-styreneformulations (commonly known as ABS), polybutylene and acrylic estermodified styreneacrylonitrile (ASA),methyl-methacrylate-styrene-butadiene terpolymers, etc. whereby thedesirable physical characteristics of flameproofing or fire retardancywill be imparted to the aforementioned materials This property willpossess special advantages when preparing plastic or resinous materialwhich will be utilized in places which may be subjected to excessiveheat or possible flame such as architectural panels for constructionwork, skydomes, skylights, wall plugs for electrical connections, ashtrays, etc. In addition, the compound when used as a constituent ofpaint, lacquer, varnishes, or protective coatings, films, etc. will alsoimpart a fire resistancy to these compounds, and, therefore, render themcommercially attractive as articles of commerce. Furthermore, the flameretardancy of foams such as the polyurethane foams will greatly enhancetheir use as insulating material or soundproofing material. Also,besides imparting the desirable physical characteristics of flameretardancy to the various articles of manufacture, the additives willrender clear plastics or resins more stable to color changes and,therefore, will be an important component of these compounds whenever itis desirable that discoloration of the finished product is to be avoidedor will tend to render such articles unuseable. It is also contemplatedthat the novel composi tions of matter of this invention may also beused as an insecticide or as an ingredient in insecticidal formulations.Furthermore, it is also contemplated that the novel compositions ofmatter of this invention may also be used as high pressure additives forlubricating oils and greases, as effective releasing agents, etc.

It is therefore an object of this invention to provide novelcompositions of matter which possess desirable physical properties.

Another object of this invention is to provide novel compositions ofmatter possessing the desirable physical characteristics offlameproofing and fire retardancy which may be used as additives inother chemical formulations.

In one aspect an embodiment of this invention resides in a novelcompound having the formula:

wool, Dacron, nylon, rayon, etc. coatings, paints, varnishes, leather,foams, cellulose acetate butyrate, ethyl cellulose, cellulosepropionate, etc., polyolefins such as polyethylene and polyethyeneco-polymers, polypropylene and polypropylene co-polymers, polystyrene,polystyrene co-polymers, polyvinyl acetate, or alcohol and co-polymers,polyesters, polyurethane, polyphenyl ethers, polycarbonates, polyamides,polyoxymethylenes, polyalkylene oxides such as polyethylene oxide,polyacrylates and coin which A, X, and Y are independently selected fromthe group consisting of hydrogen and halogen, at least one A and two Xsbeing halogen; Z is selected from the group consisting of oxygen,sulfur, amino, and lower alkyl radicals, m is an integer of from 1 to 2;n ranges from O to 2; and p ranges from 0 to 1.

Another embodiment of this invention is found in a composition of mattercomprising a polymeric compound containing at least one reactivesubstituent and a haloaryl imide of a halo-substitutedpolyhydropolycyclicdicarboxylic acid.

A specific embodiment of this invention resides in 00,11- bis[5,6,7,8,9,9 hexachloro 1,2,3,4,4a,5,8,8a octahydro 5,8 methano 2,3naphthalenedicarboximido]- 2,3,5,6-tetrachloro-p-xylene.

Another specific embodiment of this invention is found in a polymericcompound comprising polyphenylene oxide andu,u'bis-[5,6,7,8,9,9-hexachloro-l,2,3,4,4a,5,8,'8aoctahydro 5,8 methano2,3 naphthalenedicarboximido]-2,3,5, 6-tetrachloro-p-xylene.

Other objects and embodiment will be found in the following furtherdetailed description of the present invention.

As hereinbefore set forth the present invention is concerned with novelcompositions of matter comprising haloaryl imides ofpolyhalopolyhydropolycyclicdicarboxylic acids. In one embodiment, thesecompounds are prepared by condensing apolyhalopolyhydropolycyclicdicarboxylic acid or anhydride thereof with ahalo-substituted xylene-a,a-diamine or a halo-substituted p-ditolylether-, thioether-, amine-, or alkane-a,a'-diamine, details of thecondensation being set forth in a more specific manner in a latterportion of the specification. Any suitable polyhalo-substitutedpolyhydropolycyclicdicarboxylic acid or anhydride thereof may be used inthe preparation of the desired composition of matter, saidpolyhalosubstituted polyhydropolycyclicdicarboxylic acid or anhydridethereof being illustrated by the following general formulas:

in which X is selected from the group consisting of halogen andparticularly chlorine and/or bromine, and hydrogen radicals, at leasttwo of the Xs being halogen, Y is also selected from the groupconsisting of halogen and hydrogen radicals, in is an integer of fromone to two, It ranges from zero to two and p ranges from zero to one.Representative examples of the polyhalopolyhydropolycyclicdicarboxylicacids or anhydrides thereof which may be utilized includel,4,5,6,7,7-hexachlorobicyclo-[2.2.1]- 5-heptene-2,S-dicarboxylic acidor the anhydride thereof which may be prepared by condensing maleic acidor maleic anhydride with hexachlorocyclopentadiene. Another example ofthe acid or anhydride which may be used comprises 5,6,7,8,9,9 hexachloro1,2,3,4,4a,5,8,8aoctahydro 5,8 methano 2,3 naphthalenedicarboxylic acidwhich is prepared by condensing a conjugated aliphatic diene such as1,3-butadiene with maleic acid and thereafter further condensing theresultant cyclohexenedicarboxylic acid, which is1,2,3,6-tetrahydrophthalic acid, with a halocycloalkadiene such ashexachlorocyclopentadiene to form the desired product. It is to beunderstood that the corresponding anhydride may be prepared by utilizingmaleic anhydride as one of the starting materials in place of maleicacid. Yet another example of a polyhalopolyhydropolycyclicdicarboxylicacid or anhydride which may be used is one which is prepared bycondensing cyclopentadiene with maleic acid or maleic anhydride to formnorborn-5-ene-2,3dicarboxylic acid or anhydride and thereaftercondensing this product with hexachlorocyclopentadiene to form 5, 6,7,8,9,9-hexachlor0 1,2,3,4,4a,5,8,8a octahydro l,4,5,8 dimethano-2,3naphthalenedicarboxylic acid or anhydride. It is to be understoodthat other starting materials may also be utilized to form similar acidsor anhydrides. Illustrative examples of these starting materials includeother acids such as fumaric acid, itaconic acid, citroconic acid,glutaconic acid, etc.; conjugated aliphatic dienes include 2-methyl-l,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 2,4- hexadiene, 2,3dimethyl 1,3 butadiene, 1,3-heptadiene, 2,4-heptadiene; conjugatedoctadienes, nonadienes, etc.; other suitable halo-substitutedcycloalkadienes which may be used include 1,2 dichlorocyclopentadiene,1,2,3 trichlorocyclopentadiene, 1,2,3,4 tetrachlorocyclopentadiene,1,2,3,4,5 pentachlorocyclopentadiene and similar compounds in which allor part of the chlorine is replaced by other halogen atoms andparticularly bromine.

The aforementioned polyhalopolyhydropolycyclicdicarboxylic acids oranhydrides thereof are condensed with a compound possessing the genericformula:

which for purposes of this invention, are designated as halo-substitutedxylene-a,a-diamines or halo-substituted p-ditolyl ether-, thioether-,amine-, or alkane-u,a'-diamines. In the aforementioned formulae, A isselected and from the group consisting of halogen and hydrogen radicals,at least one A being halogen, preferably chlorine or bromine, and Z isselected from the group consisting of oxygen, sulfur, amino, and alkylradicals. Specific examples of these compounds will include2-chloro-pxylene-a,u-diamine, 2,3-dichloro p xylene-a,a-diamine,2,3,5-trichloro-p-xylene-a,adiamine, 2,3,5,6tetrachlorop-xylene-m,ot'-diamine; 2 bromo p xylene-a,a'-diamine,2,3dibromo-p-xylene-c d-diamine, 2,3,5 tribromo-p-xylene-a,a'-diamine,2,3,5,6-tetrabromop-xylene 0t,ot' diamine, 2,2-dichloro-p-tolylether-a,a'-diamine, 2,2,3,3'-tetrachloro-p-tolyl ether-u,a'-diamine,2,2,3,3',5,5,6,6'-octachloro-p-tolyl ether oc,oc' diamine;2,2-dihcoloro-p-tolyl thioether-u,o-diamine, 2,2',3,3'tetrachlorop-tolyl thioether 0 m diamine, 2,2',3,3,5,5,6,6octachloro-p-tolyl thioether-a,u-diamine;2,2'-dichloro-p-tolylamino-u,a-diamine, 2,2',3,3'-tetrachloro ptolylamino-a,u-diamine, 2,2,3,3',5,5',6,6'-octachloro p tolylamino 0:,a'diamine; 2,2 dichloro p tolylmethane ot,ot' diamine, 2,2',3,3tetrachloro p tolylmethane oc,ot' diamine, 2,2,3,3',5,5,6,6' octachlorop tolylmethane a,u' diamine;2,2,3,3-tetrachloro-diphenyl-2,2'-propane-a,a'-diamine;2,2-dibromo-p-tolyl ether-u,a'-diamine, 2,2,3,3- tetrabromo-p-tolylether-m,a'-diamine, 2,2,3,3',5,5',6,6- octabromo-p-tolyl ether owdiamine; 2,2 dibromo-ptolyl thioether-a,a'-diamine,2,2,3,3'-tetrabromo-p-tolyl thioether ma diamine,2,2,3,3,5,5',6,6'-octabromo-ptolyl thioether-a,a-diamine;2,2'-dibromo-p-tolylaminood-diamine, 2,2',3,3'tetrabromo-p-tolylamino-a,a'-diamine, 2,2,3,3',5,5',6,6octabromo-p-tolylamino-a,a-diamine; 2,2 dibromo p tolylmethane 0:,0z'diamine, '2,2',3,3 tetrabromo p tolylmethane 1,0! diamine,2,2,3,3,5,5',6,6' octabromo p tolylmethane 00,00 diamine; 2,2,3,3'tetrabromo diphenyl 2,2 propaneu,a'-diamine; etc. In addition, it isalso contemplated Within the scope of this invention that m-xylenes suchas 2- chloro-m-xylene-a,a'-diamine, 2,4-dichloro-m-xylene-u,u'- diamine,2,4,5-trichloro-m-xylene ,0! diamine, 2,2'-dichloro-m-ditolyl ether11,11 diamine, 2,2,4,4'-m-ditolyl ether-a,ot'-diamine,2,2'-dichloro-m-ditolyl thioether-a,a'- diamine, 2,2',4,4-m-ditolylthioether-a,a'-diamine, 2,2- dichloro-m-ditolylamine-u i-diamine,2,2,4,4-m ditolylamine-a,a-diamine, 2,2-dichloro-m-ditolylmethaneot,ct'- diamine, as well as the bromo-substituted analogs thereof mayalso be condensed with the aforementioned acids or anhydrides to preparethe novel compositions of matter of the present invention. It is to beunderstood that the aforementioned compounds are only representative ofthe class of compounds which may be used and that the present inventionis not necessarily limited thereto.

As hereinbefore set forth, the novel compositions of matter of thepresent invention are prepared by condensing apolyhalopolyhydropolycyclicdicarboxylic acid or anhydride thereof of thetype hereinbefore set forth in greater detail with a halo-substitutedxylene-a,a'-dian1ine or a halo-substituted ditolyl ether-, thioether-,amine-, or alkane-a,u-diamine at condensation conditions which include atemperature in the range of from ambient (about 25 C.) up to about 250C. or more and at a pressure which may range from atmospheric up toabout 50 atmospheres or more. In the event that elevated temperatures inthe upper limit of the aforementioned range are employed, it iscontemplated that the reaction will be effected at superatmosphericpressures. These superatmospheric pressures are generated by theintroduction of a substantially inert gas such as nitrogen into thereaction zone, said pressure which is used being that which issufficient to maintain a major portion of the reactants in the liquidphase. Generally speaking, in the preferred embodiment of the process,the reaction or condensation is effected in the presence of asubstantially inert organic solvent. Therefore, when utilizing such asolvent, the temperature which is employed will usually be that of thereflux temperature of the solvent. Specific examples of the type ofsolvents which may be employed will include aromatic hydrocarbons suchas benzene, toluene, the xylenes, ethylbenzene, etc.; aliphatic andcycloaliphatic parafiins such as n-pentane, n-hexane, n-heptane,cyclopentane, methylcyclopentane, etc.; alcohols such as methyl alcohol,ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol,etc.; ethers such as dimethyl ether, diethyl ether, dipropyl ether,etc.; the dimethyl ether of diethylene glycol, the diethyl ether ofdiethylene glycol, dioxane, various esters, chlorinated hydrocarbons,etc. The residence time during which the condensation is effected willbe of a duration which is suflicient to effect a substantially completereaction and may vary in time from about 0.5 up to about 10 hours ormore, the reaction being substantially complete when the theoreticalamount of water which has been formed during the condensation has beenrecovered. In addition, the mole ratio ofpolyhalopolyhydropolycyclicdicarboxylic acid or anhydride thereof to thediamine compound will vary over a wide range depending upon theparticular compound which is to be the desired product. Therefore, themole ratio may range from 1:1 up to about 5.1 moles ofpolyhalopolyhydropolycyclicdicarboxylic acid or anhydride thereof permole of diamine compound. For example, when the desired product willcomprise a mono-imide, the reactants will be present in a 1:1 molarratio. However, if a bis-imide is to be the final product, the acid oranhydride will be present in a molar excess ranging from 2:1 up to about5:1 moles of acid or anhydride per mole of diamine compound.

The process of the present invention may be effected in any suitablemanner and may comprise either a batch or continuous type operation. Forexample, when a batch type operation is used a quantity of theparticular acid or anhydride and diamine compound is placed in anappropriate apparatus along with a particular solvent if one is desired.The apparatus, which may comprise a condensation flask, is provided withheating and stirring means as well as a water trap whereby the water ofreaction which is formed may be withdrawn. The flask is then heated tothe desired operating temperature, which if a solvent is used, is thereflux temperature thereof, and allowed to proceed for a predeterminedresident time. This time is calculated as when the theoretical amount ofwater has been removed. Following this the flask and contents thereofare allowed to cool to room temperature and the reaction product isrecovered. The product is then separated from any solvent byconventional means as evaporation, suction, filtration, etc., andrecovered. In the event that superatmospheric temperatures and pressuresare to be used, the reactor which is employed for the batch typeoperation may comprise a rotating or stirred autoclave whereby thedesired pressure may be attained by charging nitrogen to the reactorprior to heating to the desired operating temperature.

It is also contemplated within the scope of this invention that acontinuous manner of operation may be employed. When such a type ofoperation is used the starting material comprising the acid or anhydrideof the type hereinbefore set forth in greater detail and the diaminocompound are continuously charged to the reactor which is maintained inthe proper operating conditions of temperature and pressure. In theevent that a solvent is to be employed, one or both of the reactants maybe dissolved in the solvent prior to entry into said reactor.Alternatively speaking, the solvent may be charged to the reactor in aseparate stream if so desired. Upon completion of the desired residencetime the reaction effluent is continuously withdrawn. The reactionproduct is separated from the water of reaction which is formed in thesolvent by conventional means. In addition, the reaction product is alsoseparated from any unreacted starting material which may still bepresent in the reactor, the latter being recycled to form a portion ofthe feed stock. The desired haloaryl imides of the halo-substitutedpolyhydropolycyclicdicarboxylic acids are recovered.

While the aforementioned method for preparing the novel compositions ofmatter of the present invention have illustrated the condensation of ahalo-substituted polyhydropolycyclicdicarboxylic acid or anhydride witha compound containing at least one amino substituent, it is alsocontemplated within the scope of this invention that other processes forpreparing the desired products may also be utilized. For example, thediamine compound may also be reacted with an unsaturated dibasic acid oranhydride, thereafter adding a diolefinic hydrocarbon to the resultantimide followed by further addition of a halogenated diene. For example,maleic acid or maleic anhydride may be condensed with2,3,5,6-tetrachloro-pxylene 0:,a' diamine in a mole ratio of two molesof maleic acid or maleic anhydride per mole of diamine to form abis-imide, thereafter condensing the bis-imide with 1,3 butadiene,followed by the further addition of hexachlorocyclopentadiene to form anovel composition of matter comprising ot,ot'bis-[5,6,7,8,9,9-hexachloro 1,2,3,4,4a,5,8,8a octahydro 5,8 methano 2,3-naphthalenedicarboximido] 2,3,5,6 tetrachloro pxylene.

Examples of novel compositions of matter of the present inventioncomprise haloaryl imides of polyhalopolyhydropolycyclicdicarboxylicacids. Some illustrative examples of these compounds will include aamino a- (5,6,7,8,9,9 hexachloro l,2,3,4,4a,5,8,8a octahydro- 5,8methano 2,3 naphthalenedicarboximido) 2,3- dichloro p xylene, oz amino a(5,6,7,8,9,9-hexachloro 1,2,3,4,4a,5,8,8a octahydro l,4,5,8 dimethano-2,3 naphthalenedicarboximido) 2,3 diehloro pxylene, a. amino a(1,4,5,6,7,7 hexachlorobicyclo- [2.2.1] 5 heptene 2,3 dicarboximido) 2,3di- 7 chloro p xylene, a amino c (5,6,7,8,9,9-hexachloro1,2,3,4,4a,5,8,8a octahydro 5,8 methano- 2,3 naphthalenedicarboximido)2,3,5,6 tetrachlorop xylene, a amino u (5,6,7,8,9,9 hexachloro-1,2,3,4,4a,5,8,8a octahydro l,4,5,8 dimethano 2,3-naphthalenedicarboximido) 2,3,5,6 tetrachloro pxylene, oz amino a(1,4,5,6,7,7 hexachlorobicyclo- [2.2.1] heptene 2,3 dicarboximido)2,3,5,6- tetrachloro p xylene, 0c amino oc' (5,6,7,8,9,9- hexachloro1,2,3,4,4a,5,8,8a octahydro 5,8 methano- 2,3 naphthalenedicarboximido)2,4 dichloro mxylene, o5 amino a (5,6,7,8,9,9 hexachloro-1,2,3,4,4a,5,8,8a octahydro 1,4,5,8 dimethano 2,3-naphthalenedicarboximido) 2,4 dichloro m xylene, a amino a (l,4,5,6,7,7hexachlorobicyclo-[2.2.1]- 5 heptene 2,3 dicarboximido) 2,4 dichloromxylene, a amino a (5,6,7,8,9,9 hexachloro- 1,2,3,4,4a,5,8,8a octahydro5,8 methano 2,3- naphthalenedicarboximido) 2,4,S,6 tetrachloro mxylene,0c amino a (5,6,7,8,9,9 hexachloro- 1,2,3,4,4a,5,8,8a octahydro 1,4,5,8dimethano 2,3- naphthalenedicarboximido) 2,4,5,6 tetrachloro mxylene, aamino a (l,4,5,6,7,7 hexachlorobicyclo- [2.2.1] 5 heptene 2,3dicarboximido 2,4,5,6- tetrachloro m xylene, a amino a (5,6,7,-8,9,9'-hexachloro 1,2,3,4,4a,5,8,8a octahydro 5,8 methano- 2,3naphthalenedicarboximido) 2,2,4,4 tetrachloroditolyl ether, or amino a(5,6,7,8,9,9 hexachloro- 1,2,3,4,4a,5,8,8a octahydro l,4,5,8 dimethano2,3- naphthalenedicarboximido) 2,2,4,4 tetrachloroditolyl ether, oramino a (l,4,5,6,7,7-hexachlorobicyclo- [2.2.1] 5 heptene 2,3dicarboximido) 2,2,4,4,- tetrachloroditolyl ether, 0c amino a(5,6,7,8,9,9 hexachloro .1,2,3,4,4a,5,8,'8a octahydro 5,8 methano- 2,3naphthalenedicarboximido) 2,2,4,4' tetrachloroditolyl thioether, a aminoa (5,6,7, 8,9,9 hexachloro 1,2,3,4,4a,5,8,8a octahydro1,4,5,8-dimethano- 2,3 naphthalenedicarboximido)2,2,4,4-tetrachloroditolyl thioether, a amino a (1,4,5,6,7,7hexachlorobicyclo [2.2. 1] 5 heptene 2,3 dicarboximido)- 2,2',4,4tetrachloroditolyl thioether, a amino a- (5,6,7,8,9,9 hexachloro1,2,3,4,4a,5,8,8a octahydro- 5,8 methano 2,3 naphthalenedicarboximido)2,2, 4,4 tetrachloroditolylamine, oz amino a (5,6, 7,8,9,9 hexachloro1,2,3,4,4a,5,'8,8a octahydro- 1,4,5,8 -dimethano 2,3naphthalenedicarboximido)- 2,2,4,4-tetrachloroditolylamine,u-amino-oc-(1,4,5,6,7,7- hexachlorobicyclo [2.2.1]-5-heptene-2,3-dicarboximido 2,2,4,4-tetrachloroditolylamine,u,ot-bis-(5,6,7,8,9,9-hexachloro 1,2,3,4,4a,5,8,8a octahydro 5, 8methano- 2,3 naphthalenedicarboximido) 2,3 tetrachloro pxylene, ot,oc'bis (5,6,7,8,9,9 hexachloro 1,2,3,4,4a, 5,8,8a octahydro 1,4,5,8dimethano 2,3 naphthalenedicarboximido) 2,3 tetrachloro p xylene,

ot,a' bis (1,4,5,6,7,7 hexachlorobicyclo [2.2.1]-5- heptene 2,3dicarboximido) 2,3 tetrachloro pxylene, ot,oc' bis (5,6,7,'8,9,9hexachloro 1,2,3,4,4a, 5,8,8a octahydro 5,8 methane 2,3naphthalenedicarboximido) 2,3,5,6 tetrachloro p xylene, u bis-(5,6,7,8,9,9 hexachloro l,2,3,4,4a,5,8,8a octahydro- 1,4,5,8 dimethano2,3 naphthalenedicarboximido)- 2,3,5,6 tetrachloro p xylene, 0 m bis(1,4,5,6,7,7- hexachlorobicyclo [2.2.1] 5 heptene 2,3 dicarboximido)2,3,5,6 tetrachloro p xylene, 4,4-bis- (5,6,7,8,9,9 hexachlorol,2,3,4,4a,5,8,8a octahydro- 5,8 methano 2,3naphthalenedicarboximidomethyl)- 2,2,3,3,5,5,6,6' octachlorodiphenylether, 4,4 bis- (5,6,7,8,9,9 hexachloro l,2,3,4,4a,5,8,8aoctahydrol,4,5,8 dimethano 2,3 naphthalenedicarboximidomethyl)2,2,3,3,5,5,6,6 octachlorodiphenyl ether, 4,4 bis (1,4,5,6,7,7hexachlorobicyclo [2.2.1] 5- heptene 2,3 dicarboximidomethyl)2,2,3,3,5,5,6,6- octachlorodiphenyl ether, 4,4 bis (5,6,7,3,9,9hexachloro 1,2,3,4,4a,5,8,8a octahydro 5,8 methano- 2,3naphthalenedicarboximidomethyl) 2,2',3,3,5,5,

8 6,6 octachlorodiphenylamine, 4,4 bis (5,6,7,8,9,9- hexachlorol,2,3,4,4a,5,8,8a octahydro l,4,5,8 dimethano 2,3naphthalenedicarboximidornethyl)-2,2', 3,3,5,5,6,6,octachlorodiphenylamine, 4,4 bis (1,4, 5,6,7,7 hexachlorobicyclo [2.2.1]5 heptene 2,3- dicarboximidomethyl) 2,2, 3,3,5,5,6,6octachlorodiphenylamine, 4,4 bis (5,6,7,8,9,9 hexachloro 1,2, 3,4,4a,5,8,8a octahydro 5,8 methano 2,3 naphthalenedicarboximidomethyl)2,2,3,3,5,5,6,6 octachloro 2,2 diphenylpropane, 4,4 bis (5,6,7,8,9,9-hexachloro l,2,3,4,4a,5,8,8a octahydro 1,4,5,8 dimethano 2,3naphthalenedicarboximidomethyl) 2,2, 3,3,5,5,6,6' octachloro 2,2diphenylpropane, 4,4- bis-(1,4,5,6,7,7 hexachlorobicyclo [2.2.1] 5heptene- 2,3 dicarboximidomethyl) 2,2',3,3,5,5,6,6 octachloro 2,2diphenylpropane, 4,4 bis (5,6,7,8,9,9- hexachloro l,2,3,4,4a,5, 8,8aoctahydro 5,8 methano- 2,3 naphthalenedicarboxirnidomethyl)2,2',3,3,5,5, 6,6 octachlorodiphenyl thioether, 4,4 bis (5,6,'7,'8, 9,9hexachloro 1,2,3,4,4a,5,8,8a octahydro l,4,5,8-

' dimethano 2,3 naphthalenedicarboximidomethyl)-2,2',

3,3',5,5,6,6 octachlorodiphenyl thioether, 4,4 bis- (1,4,5,6,7,7hexachlorobicyclo [2.2.1] 5 heptene- 2,3 dicarboximidomethyl)2,2/,3,3',5,5,6,6-octachl0rodiphenyl thioether; the bromo-substitutedanalogs thereof, etc. While the above illustrative examples are alldrawn to hexahalo-substituted polycyclic portions of the novel compound,it is to be understood that imides containing less than six halogenatoms in the aforementioned cyclic portion such as the pentachloro-,pentabrom0-, tetrachloro-, tetrabromo-, trichloro-, tribromo-,dichloro-, and dibromo-substituted compounds also fall within the scopeof this invention and are correspondingly prepared by using apentahalo-, tetrahalo-, trihalo-, or dihalo-substituted dienichydrocarbon as starting materials.

As hereinbefore set forth, the novel compositions of matter of thepresent invention may be utilized as additives for plastics, resins,polymers, co-polymers, textiles, naturally occurring products such asleather, wood, paints, coatings, etc. For example, the haloaryl imidesof the halo substituted polyhydropolycyclicdicarboxylic acids may beused as additives with polymeric olefins such as polypropylene wherebythe final product will possess advantageous physical properties such asan increased stability against deterioration, weathering, and agingwhich has been induced by chemical, physical, biological agents, orradiation. In addition, the polyolefins will have a higher ignitionpoint as well as a high degree of flame retardancy. The imides may beadded to polypropylene in a range of from about 2% to about 30% byweight of the polymeric material to be treated. Thereafter it will befound that the oxygen index will have increased while the burning ratewill be decreased. Examples of other polymeric products which may betreated with the haloaryl imides of the halo-substitutedpolyhydropolycyclicdicarboxylic acids will include epoxy resins such asthe condensation product of epichlorohydrin and bis-phenol- A. The epoxyresins in an uncured state will usually be thermal plastic and may rangefrom low viscosity liquids to high melting point brittle solids. Theresins may be cured by mixing a curing agent such as phthalic anhydridewith the resin, admixing the resultant mixture with an imide of the acidof the type hereinbefore set forth and thereafter curing the mixture bytreatment at an elevated temperature for a predetermined period of time.The resultant product will have the physical characteristics thereofaltered to their desirable values as pertains to color stability andflame retardancy and thus may be utilized for various purposes such asfioor surfacings, coatings, etc. Other types of polymeric compoundswhich may be treated with the novel compositions of matter of thepresent invention will include polyphenyl ethers (polyphenylene oxides)which have been modified by treatment with styrene, polycarbonates,polyesters, polyurethane foams, etc.

It is also contemplated within the scope of this inven tion that otherconventional flame retardants including, but not limited to, phosphateesters, alkyl diaryl phosphates, cresol diphenyl phosphate, octyldiphenyl phosphate, triaryl phosphates, tributyl phosphate, triphenylphosphate, phosphonate esters, antimony oxide, barium metaborate, zincborate, boric acid, dibutyl tin maleate, etc. may be used in conjunctionwith the haloaryl imides of halo-substitutedpolyhydropolycyclicdicarboxylic acids of the present invention.

The following examples are given to illustrate the process of thepresent invention which, however, are not intended to limit thegenerally broad scope of the present invention in strict accordancetherewith.

EXAMPLE I In this example 68.5 grams (0.25 mole) of 2,3,5,6-tetrachloro-p-xylene-u,ot'-diamine along with 212.5 grams (0.5 mole) of5,6,7,8,9,9-hexachloro 1,2,3,4,4a,5,8,8aoctahydro 5,8 methano 2,3naphthalenedicarboxylic anhydride plus about 200 cc. of xylene wererefluxed. During this time, a negligible amount of water was distilledover. Following this 200 grams of o-dichlorobenzene were added and themixture was transferred to a two-liter, three-necked flask to facilitatemixing. The mixture was again heated to reflux until the water ofaddition which was formed had been condensed out. Following this, thereflux was discontinued, the precipitate which formed was filtered off,washed with benzene and methanol, and dried for a period of 16 hours.Following this, the desired product which compriseda,a'-bis-[;'5,6,7,8,9,9-hexachloro-1,2,3,4,4a,5,8,8a-octahydro-5,8-methano 2,3-naphthalenedicarboximido]-2,3,5,6 tetrachloro-p-xylene was subjected toanalysis.

Calculated for C H Cl O N (percent): Cl, 52.2; N, 2.58. Found (percent):C], 51.8; N, 2.29. In addition, the melting point was in excess over 370C. with no color change or sublimation up to this point.

EXAMPLE II In this experiment 68.5 grams (0.25 mole) of 2,3,5,6-tetrachloro-p-xylene-oad-diamine and 218 grams (0.5 mole) of 5,6,7,8,9,9hexachloro 1,2,3,4,4a,5,8,8a-octahydro 1,4,5,8dimethano-2,3-naphthalenedicarboxylic anhydride along with 200 cc. ofxylene and 200 grams of o-dichlorobenzene are refluxed in a two-literflask provided with heating and stirring means for a period of about 8hours. During this time, the water of addition which is formed isdistilled over, the reaction being complete when no additional water hascondensed out. At this point, heating is discontinued and the mixture isallowed to return to room temperature. The precipitate wrich has formedduring the reaction is filtered, washed with benzene and methanol anddried for a period of 16 hours. The crystalline material which isrecovered comprises the desired product, namely, a,ot'bis-[5,6,7,8,9,9-hexachloro-1,2,3,4,4a,5,8,8a-octahydro 1,4,5,8dimethano-2,3-naphtha1enedicarboximido] 2,3,5,6 tetrachlorop-xylene.

EXAMPLE III A mixture of 319 grams (0.5 mole) of l,4,5,6,7,7-hexabromobicyclo [2.2.1] heptene-2,3-dicarboxylic anhydride, 68.5 grams(0.25 mole) of 2,3,5,6-tetrachlorop-xylene-u,af-diamine, 200 grams ofo-dichlorobenzene, and 300 cc. of xylene is treated in a manner similarto that set forth in the above examples. After heating the mixture to areflux temperature until no additional water of condensation isrecovered, the mixture is allowed to cool to room temperature andfiltered. The crystalline precipitate is washed with benzene andmethanol and thereafter dried for a period of about 12 hours. Therecovered crystalline material comprises a,oc'-biS-(1,4,5,6,7,7-hexabromobicyclo-[2.2.1] 5 heptene-2,3-dicarboximido)-2,3,5,6-tetrachloro-p-xylene.

10 EXAMPLE IV A mixture of 212.5 grams of 5,6,7,8,9,9-hexachloro-1,2,3,4,4a,5,8,8a octahydro 5,8 methano-2,3-napthalenedicarboxylicanhydride, 126 grams (0.25 mole) of 2,2,3,3,5,5,6,6' octachloro-p-tolylether-a,a-diamine, 200 grams of o-dichlorobenzene and 300 cc. of xyleneis refluxed for a period of 8 hours until the water of condensation hasceased to form. The precipitate which forms during the reaction isfiltered from the mother liquor, washed with benzene and methanol andallowed to dry for a period of about 12 hours. This material comprisingthe desired product is 4,4'-bis-[5,6,7,8,9,9 hexachloro-1,2,3,4,4a,5,8,8a-octahydro 5,8 methano-2,3-naphthalenedicarboximidomethyl]-2,2,3,3',5,5',6,6' octachlorodiphenyl ether.

EXAMPLE V In this example a mixture of 212.5 grams (0.05 mole) of5,6,7,8,9,9 hexachloro 1,2,3,4,4a,5,8,8a-octahydro-5,8-methano-2,3-naphthalenedicarboxylic anhydride, 126 grams (0.25 mole)of 2,2',3,3',5,5,6,6-octachloroditolylamine-o eU-diamine, 200 grams ofo-dichlorobenzene, and 300 cc. of xylene is refluxed for a period oftime sufiicient to complete the reaction, the completion of the reactionbeing evidenced by the fact that no additional water of condensation isformed. The resultant crystalline material is separated from the motherliquor, washed with benzene and dried. The crystalline materialcomprising the desired product, namely,4,4-bis-[1,4,5,6,7,7-hexachlorobicyclo [2.2.1] 5heptene-2,3-dicarboximidomethyl] 2,2',3,3,5,5',6,6octachlorodiphenylamine, is recovered.

EXAMPLE VI A mixture of 346 grams (0.5 mole) of 5,6,7,8,9,9-hexabrorno-l,2,3,4,4a,5,8,8a-octahydro 5,8 methano-2,3-naphthalenedicarboxylic anhydride, 132.5 grams (0.25 mole) of2,2',3,3,5,5',6,6-octachloroditolyl-2,2-propanem,u'-diarnine, 200 gramsof o-dichlorobenzene, and 300 cc. of xylene is treated in a mannersimilar to that set forth above. After said treatment, the desiredproduct comprising 4,4 bis-[5,6,7,8,9,9-hexabromo-1,2,3,4,4a,5,8,8a-octahydro 5,8 methano-2,3-naphthalenedicarboximidomethyl]2,2,3,3,5,5,6,6 octachloro 2,2 diphenylpropaue is recovered.

EXAMPLE VII In this example a mixture comprising 194.5 grams (0.5 mole)of l,4,5,6,7,7-hexachlorobicyclo-[2.2.1]-5- heptene-2,3-dicarboxylicacid, 130 grams (0.25 mole) of 2,2,3,3',5,5,6,6-octachloro p ditolylthiO6thI'-a,oc'-diamine, 200 grams of o-dichlorobenzene, and 200 cc. ofxylene is heated to reflux for a period of about 6 hours. During thistime, all of the water of condensation which is formed is withdrawn andcollected. When the formation of the water of condensation has ceased,the mixture is allowed to cool to room temperature. The crystallinematerial is separated from the mother liquor by filtration, washed withbenzene and methanol, and thereafter dried and collected. Thiscrystalline material comprises 4,4 bis(l,4,5,6,7,7-hexachlorobicyclo-[2.2.l]-5-heptene 2,3dicarboximidomethyl)-2,2,3,3',5,5',6,6'-octachlorodiphenyl thioether.

EXAMPLE VIII A liquid epoxy resin having an epoxide equivalent weight ofand known in the trade as Epon 828 is admixed with phthalic anhydrideand 4,4-his-[5,6,7,8,9,9- hexachloro 1,2,3,4,4a,5,8,8a octahydro 5,8methano 2,3 naphthalenedicarboximidomethyl] 2,2,3,3,5,5,6,6'-0ctachlorodiphenyl ether. The mixture is heated until said mixturebecomes homogeneous and is poured into molds which are prepared fromglass sheets using Teflon spacers. In addition, a mold release agent isalso used to facilitate removal of the cured resins from the molds. Themolds are placed in an air-circulating oven and allowed to cure for aperiod of about six hours at a temperature of 110 C. By utilizingvarious widths of spacers, sheets of various thickness are prepared. Thesheets are then removed from the mold and cut into strips and areevaluated for flame retardancy. In addition to possessing excellent heatdistortion temperatures and hardness, as measured by a Shore Durometer,the cured resin will be found to be self-extinguishing when removed fromdirect action of a flame.

EXAMPLE IX In like manner, a mixture comprising 150 grams of a polymercomprising polyphenyl ether (polyphenylene oxide) which has beenmodified with styrene and 50 grams of C'.,OL' bis [5,6,7,8,9,9hexachloro 1,2,3,4,4a,5,8,8aoctahydro 5,8 methano 2,3naphthalenedicarboximido]-2,3,4,6-tetrachloro-p-xylene are admixed at anelevated temperature in order to insure that the mixture is homogeneous.After the mixture is poured into molds and allowed to cool, theresulting composition of matter, upon testing, will be found to beself-extinguishing when re moved from the direct action of a flame, thusillustrating the flame retardancy properties of the treated polyphenylethers.

Likewise, polycarbonates, when treated with the compositions of mattercomprising the haloaryl imides of thepolyhalopolyhydropolycyclicdicarboxylic acids will also exhibitflame-retardant properties, the treated polymers beingself-extinguishing when removed from the action of a flame. In addition,the aforesaid compounds including, but not limited to, the epoxy resins,polycarbonates, polyolefins, polyesters, acrylic plastics, etc., whichare treated by the addition of the haloaryl imides herein described ingreater detail, will also exhibit greater stability as regards colorwhen exposed to the direct action of sunlight over a period of time.

EXAMPLE X In the example 14.5 grams of u,a-bis[5,6,7,8,9,9-hexa chloro1,2,3,4,4a,5,8,8a octahydro 5,8 methano 2,3 naphthalenedicarboximido]2,3,5,6 tetrachloro p xylene which was prepared according to Example Iabove was milled with 85.5 grams of a commercial high molecular weightpolypropylene and 0.5 grams of a polyhydroxypolycyclic butane oxidationinhibitor, said milling being accomplished for a period of live minutesat 185 C. The treated polypropylene was cut into strips which containeda glass cloth in the center of the strip to prevent dripping during thecombustion. A strip of this treated polypropylene was then burned in anapparatus similar to the one described by C. P. Fenimore and J. F.Martin in the November 1966 issue of Modern Plastics. The polypropylenecontaining the haloaryl imide of thepolyhalopolyhydropolycyclicdicarboxylic acid had an oxygen index (thelowest mole fraction of oxygen sufficient to maintain combustion)n=0.l85. A similar strip of polypropylene which was milled with theoxidation inhibitor but did not contain the flame retardant compoundwhen burned had an oxygen index of 0.180. A further difference wasillustrated by the fact that the rate of combustion of the polypropylenecontaining the haloaryl imide was 190 seconds per inch of sample. Thepolypropylene sample which did not contain the haloaryl imide had a rateof combustion of 55 seconds per inch. This illustrates the flameretarding properties of the aforementioned oc,o'-biS-[5,6,7,8,9,9-h6X-achloro 1,2,3,4,4a,5,8,8a octahydro 5,8 methano 2,3naphthalenedicarboximido] 2,3,5,6 tetrachloro p-xylene.

EXAMPLE XI A commercial acrylonitrile-butadiene-styrene copolymer, aftermilling with an oxidation inhibitor, was pressed in strips as describedabove with glass cloth in the center of the strip to prevent drippingduring the combustion. In a second sample, 75 grams of the ABS wasmilled with 25 grams ofaged-bis-[5,6,7,8,9,9'-hexachloro-1,2,3,4,4a,5,8,8aoctahydro-1,4,5,8-dimethano2,3 naphthalenedicarboximido]-2,3,5,6tetrachloro-p xylene and 0.15 gramof a in which A, X, and Y are independently selected from the groupconsisting of hydrogen and halogen, at least one A and two Xs beinghalogen; Z is selected from the group consisting of oxygen, sulfur,amino, and lower alkyl radicals, m is an integer of from 1 to 2; nranges from 0 to 2; and p ranges from 0 to 1.

2. The compound as set forth in claim 1, further characterized in thatsaid halogen is chlorine.

3. The compound as set forth in claim 1, further characterized in thatsaid halogen is bromine.

4. The compound of claim 1 being a,oc'-biS[5,6,7,8,9,9-hexachloro-1,2,3,4,4a,5,8,8a-octahydro-5,8 methano-2,3-naphthalenedicarboximido] -2,3 ,5 ,6-tetrachloro-p-xylene.

5. The compound of claim 1 being ot,a'-biS-[5,6,7,8,9,9hexachloro-1,2,3,4,4a,5,8,8a-octahydro-1,4,5,8-dimethano-2,3-naphthalenedicarboximido] 2,3,5,6-tetrachloro-p-xyl ene.

6. The compound of claim 1 being a,a'-bis(1,4,5,6,7,7- hexabromobicyclo[2.2.1]-5-heptene-2,B-dicarboximido)- 2,3,5,6-tetrachloro-p-xylene.

methyl)-2,2,3,3,5,5',6,6'-0ctach1orodiphenyl thioether. 15

References Cited UNITED STATES PATENTS Latos et a1. 25234 Hayes 260-326Latos et al 260326 Hayes 26047 Roberts et a1 260326 ALEX MAZEL, PrimaryExaminer.

J. A. NARCAVAGE, Assistant Examiner U.S. C1. X.R.

Notice of Adverse Decision in Interference In Interference No. 98,213involving Patent No. 3,574,230, H. A. Cyba,POLYHALOPOLYHYDROPOLYCYCLICDICARBOXYLIC ACID IM- IDES, final judgmentadverse to the patentee was rendered Oct. 9, 1975, as to claim 4:.

[Official Gazette March 23, 1976.]

